Greenman and following have it right. In most applications, the wires in the cable are Black = Hot (Line), White = Neutral, and Bare = Ground. There should never be any current flowing in the Ground lead, so make no connections to it other than having it connected to the fixture mounting box.
A plain switch (such as you have in the box) needs no power. What is already installed is a normal way to do things. The power comes first to the light fixture mounting box, then a single 14/2 cable (14 gauge wires, 2 conductors plus bare Ground) is run to the switch mounting box, with Black connected to Black. But then the slightly-atypical connection is made to use the WHITE wire in that cable to bring the power back from the switch output to the Hot terminal of the light fixture; thus, that one White line is NOT a Neutral line, it is a switch output.
The Sonoff unit you bought has an extra requirement beyond those of a plain switch. It needs electrical power itself to run its electronics, so it needs access to BOTH a Hot and a Neutral connection. Right now your existing switch box does not have those leads coming to it, so that Sonoff unit cannot get power to work properly. To do this right, you will need to do some re-wiring to provide for those needs. NOTE!! Turn off ALL power to this circuit at the breaker box before opening and working!
The simplest way, which I have done, requires that you be able to add an extra cable from the lighting fixture box to the switch box. If you can do that, the straightforward version is to leave the original 14/2 cable in place and add one more just like it. In this arrangement, the old cable becomes solely the supply of Hot, Neutral and Ground to the switch box, and the new cable will serve as means of returning the switch Hot output to the light fixture, with all the Neutrals joined also.. DISconnect the White wire coming back from the old cable (from the switch) from the light fixture Hot terminal. There should already be a short White wire from the power source cable's White to the Neutral terminal of the light fixture. Now connect the White of the new cable with the White of the old cable, the White from the incoming power source, and the short White to the fixture. Connect the Black from the new cable only to the Hot terminal of the light fixture. Grounds for all three cables are twisted together and tied down to the box's Ground screw. Now at the Swtich box you will REPLACE the old switch with this Sonoff unit. That might be a problem because the unit may not fit the standard mounting box, but more on that later. The OLD cable must go to the Sonoff unit's INPUT terminals - Black to L, White to N. Its bare Ground twists with the other bare ground and they get screwed to the box's Ground screw at back. The Black of the NEW cable goes to the Sonoff's L OUTPUT terminal, and the new cable's White goes to the N Output.
When I have done this type of job, it has been easy for me to remove the original old 14/2 cable and install in its place a 14/3 cable that has an additional Red wire in it. Then you don't have an extra White wire to connect at both ends, nor is there a second bare Ground wire. The Black from the 14/3 cable is the power SUPPLY going from the fixture box's supply line to the switch box, and in your case would go to the Sonoff's INPUT L terminal. The RED in the cable goes to the Sonoff's L OUTPUT terminal to take power back to the fixture box, and there it is the one connected to the Hot terminal of the fixture. In the switch box, the incoming White goes to the Sonoff unit's N INPUT terminal, and there is nothing connected to the Sonoff's N Output terminal.
If the Sonoff unit does not fit your existing switch mounting box you might be able to adapt it to fit anyway. Be aware that, once this Sonoff unit replaces your old manual switch, it does NOT appear to have a manual switch button on it. So the ONLY way to switch that light on and off is by using the Wifi control signals that the Sonoff unit requires.
IF you want an additional manual switch in parallel with the Sonoff unit, so you can switch it on manually, you'll need moire installation work.